Formulation component

ABSTRACT

The present invention relates to agrochemical compositions comprising certain benzamide compounds and to the use of those benzamide compounds as adjuvants, especially in formulations,in particular in agrochemical formulations and in environmentally friendly formulations. The invention further extends to certain novel benzamide compounds and a process to prepare such novel compounds.

The present invention relates to agrochemical compositions comprisingcertain benzamide compounds and to the use of those benzamide compoundsas adjuvants, especially in formulations, in particular in agrochemicalformulations and in environmentally friendly formulations. The inventionfurther extends to certain novel benzamide compounds.

The efficacy of the active ingredients (AIs) in an agrochemicalcomposition can often be improved by the addition of furtheringredients. The observed efficacy of the combination of ingredients cansometimes be significantly higher than that which would be expected fromthe individual ingredients used (synergism). Typically, an adjuvant is asubstance which can increase the biological activity of an Al but isitself not significantly biologically active. The adjuvant is often asurfactant, and can be included in the formulation or added separately,e.g. by being built into emulsion concentrate formulations, or as tankmix additives.

In addition to the effect on biological activity, the physicalproperties of an adjuvant are of key importance and must be selectedwith a view to compatibility with the formulation concerned. Forinstance, it is generally simpler to incorporate a solid adjuvant into asolid formulation such as a water-soluble or water-dispersible granule.In general adjuvants rely on surfactant properties for biologicalactivity enhancement and one typical class of adjuvants involves analkyl or aryl group to provide a lipophilic moiety and a (poly)ethoxychain to provide a hydrophilic moiety. Much has been published on theselection of adjuvants for various purposes, such as Hess, F. D. andFoy, C. L., Weed technology 2000, 14, 807-813.

The present invention is based on the discovery that certain benzamidecompounds, in particular those comprising alkyl and/or alkoxylatedchains, are surprisingly effective adjuvants, significantly enhancingthe biological activity of active ingredients, in particularagrochemicals.

EP0044955 describes liquid herbicidal compositions based on a mixture ofpyidazone derivatives and biscarbamates dissolved in an acid amide.These liquid compositions are said to have improved stability: the acidamide has a low water solubility thus minimising the tendency for theactive ingredient to crystalise out, and stability of the biscarbamatein the solution is good.

WO2011/010082 describes the use of certain benzamides as solvents, inparticular for agrochemicals.

WO2006/127399 describes high load concentrate compositions comprisingthe active ingredient metaflumizone, an optional bridging agent, asurfactant and a suitable carrier solvent. N,N-diethyl-m-toluamide ismentioned as a suitable carrier solvent.

None of the above-mentioned prior art describes the use of compounds offormula (I) as described herein as adjuvants, in particular asbioefficacy adjuvants, for agrochemicals, i.e. as compounds capable ofenhancing the biological efficacy of an agrochemical.

In a first aspect, the invention provides for the use of a compound offormula (I) as an adjuvant,

wherein m is an integer of 1, 2, or 3; n is an integer of 0, 1, 2, or 3;R¹ is C(O)NR³R⁴; each R² is independently C₁₋₁₅ alkyl, each R³ isindependently H, or C₁₋₆ alkyl, each R⁴ is independently C₁₋₈ alkyl, thegroup the group-[AO]_(x)—R⁵, wherein x is an integer of 0 to 20, each Ais independently C₁₋₄ alkyl, and each R⁵ is independently H, C₁₋₄ alkyl,or NH₂.

Certain compounds of formula (I) are novel and as such form furtheraspects of the present invention. Thus the invention also provides acompound of formula (I)

wherein m is an integer of 1, 2, or 3; n is an integer of 0, 1, 2, or 3;R¹ is C(O)NR³R⁴; each R² is independently C₁₋₁₅ alkyl, each R³ isindependently H, or C₁₋₆ alkyl, each R⁴ is independently C₁₋₈ alkyl, thegroup-[AO]_(x)—R⁵, wherein x is an integer of 0 to 20, each A isindependently C₁₋₄ alkyl, and each R⁵ is independently H, C₁₋₄ alkyl, orNH₂; provided that when m is 1 and n is 1: (i) when R² is methyl in themeta position then R³ is not ethyl when R⁴ is ethyl, and R³ is notmethyl when R⁴ is methyl; (ii) when R² is methyl in the ortho positionthen: R³ is not methyl when R⁴ is propyl or tert-butyl, R³ is notn-propyl when R⁴ is ethyl, n-propyl, or n-butyl, R³ is not n-butyl whenR⁴ is methyl, ethyl or n-butyl, R³ is not iso-butyl when R⁴ isiso-butyl, R⁴ is not methyl when R³ is H, propyl, tert-butyl, orn-pentyl, R⁴ is not n-propyl when R³ is ethyl, R⁴ is not n-butyl when R³is ethyl, R⁴ is not pentyl when R³ is H or methyl, R⁴ is not2-ethyl-hexyl when R³ is H or methyl; and (iii) when R² is methyl at thepara position or ethyl at the ortho position, R³ and R⁴ are not bothmethyl.

In further aspects the invention provides a compound of formula (I) asdefined hereinbefore, wherein at least one R⁴ is the group-[AO]_(x)—R⁵,as well as a compound of formula (I) as defined hereinbefore wherein atleast one R² is at the para position.

In yet further aspects, the invention provides (a) an agrochemicalcomposition comprising a novel compound of formula (I) as definedhereinbefore in combination with an agrochemical; (b) a method of makingan agrochemical composition comprising combining a novel compound offormula (I) with said agrochemical; and (c) the use of an agrochemicalcomposition of the invention in controlling pests.

Alkyl groups and moieties are straight or branched chains, and unlessexplicitly stated to the contrary, are unsubstituted. Examples of alkylgroups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl and pentadecylgroups.

In particularly preferred embodiments of the invention, the preferredvalues for m, n and x, as well as the preferred groups for R¹, R², R³,R⁴, R⁵, and A, in any combination thereof, are as set out below.

As stated above the value of m is stated as 1, 2, or 3. Furthermore, thevalue of n is also stated as 1, 2, or 3. In one set of embodiments, thesum of the values of n and m will be 3 or greater, i.e. this encompassescompounds of formula (I) wherein m is 1 and n is either 2 or 3, as wellas compounds of formula (I) wherein n is 1 and m is either 2 or 3.

In some embodiments m is 1 or 2, more preferably 1. In some embodimentsn is 0, 1 or 2, more preferably 1. In further embodiments, both n and mare 1. In still further embodiments n is 0 and m is 1. In embodimentswherein at least one R⁴ group is -[AO]_(x)R⁵, it is preferred that n is0 or 1. In embodiments where m is 1 and R⁴ is not -[AO]_(x)R⁵, it ispreferred that n is 1.

R² is defined above as the group C₁₋₁₅ alkyl and where n is greater than1, each R² group is independently defined as such.

It is preferred that each R² group is independently a C₁₋₁₂ alkyl group,and in particularly preferred embodiments each R² is independentlymethyl, or C₆₋₁₂ alkyl, more preferably methyl or a straight chain C₆₋₁₂alkyl group, even more preferably a methyl, hexyl, octyl, decyl ordodecyl, and most preferably a methyl or dodecyl group.

In further preferred embodiments at least one R² group will be presentat the para position.

When n is 1, R² may be as defined above, however, in some embodiments itis preferred that when R² is at the ortho or para position it is a C₂₋₁₂alkyl group, more preferably a C₆₋₁₂ alkyl group, more preferably stilla straight chain C₆₋₁₂ alkyl group, and most preferably a hexyl, octyl,decyl or dodecyl group.

R¹ is defined herein as the group C(O)NR³R⁴, wherein each R³ isindependently H, or C₁₋₆ alkyl and each R⁴ is independently C₁₋₈ alkyl,or the group-[AO]_(x)R⁵, wherein x is an integer of 0 to 20, each A isindependently C₁₋₄ alkyl and each R⁵ is independently H, C₁₋₄ alkyl, orNH₂

Preferably in at least one R¹ group, R³ is selected from the groupconsisting of H, methyl, ethyl, propyl or butyl; more preferably H,methyl ethyl, n-propyl, n-butyl or iso-butyl, more preferably still H orethyl, and most preferably H.

Preferably in at least one R¹ group, R⁴ is selected from the groupconsisting of C₂₋₈ alkyl and the group-[AO]_(x)R⁵, wherein A, x and R⁵are as defined above. In further preferred embodiments x is 1 orgreater, preferably 2 or greater, more preferably 2, 4, 5, 6, 7, 8, 9,10, 11, 12, 13, 18 or 19.

The skilled man will appreciate that since the value of x can be up to20, and since each A may independently be methyl, ethyl, propyl orbutyl, the substructure -[AO]_(x)— may comprise methoxy, ethoxy, propoxyand/or butoxy units in any combination up to a tridecamer, and alsoincludes polymethoxylate chains, polyethoxylate, polypropoxylate chains,and polybutoxylate chains up to 20 units in length.

Preferably at least one A group will be ethyl or propyl. In one set ofpreferred embodiments x is an integer of 7-18 inclusive, and in aparticularly preferred set of embodiments x is an integer of 7-18inclusive and each A group is ethyl.

In a further set of preferred embodiments A is ethyl, x is 7 or 8, andR⁵ is NH₂. In a further set of preferred embodiments R⁴ will be thegroup

wherein ‘a’, ‘b’ and ‘c’ are integers and the sum of ‘a’, ‘b’ and ‘c’ isequivalent to the value of x as defined hereinbefore. In particularlypreferred embodiments, ‘b’ has a value of 9 and the sum of ‘a’ and ‘c’is approximately 3 or 4.

As stated above, each R⁵ is independently selected from the groupconsisting of H, C₁₋₄ alkyl, and NH₂ Unless stated otherwise herein inrespect of specific embodiments, it is preferred that R⁵ is selectedfrom the group consisting of H, ethyl, propyl or NH₂, more preferably Hor NH₂.

Illustrative examples of compounds for use as adjuvants in the presentinvention are given in Table 1 below, which also shows selected ¹H NMR(400 MHz) data, all obtained with CDCl₃ as the solvent. The followingabbreviations are used throughout this description:

“NMR”=nuclear magnetic resonance spectrum.

s = singlet br = broad d = doublet dd = doublet of doublets t = tripletq = quartet m = multiplet ppm = parts per million

TABLE 1 Adjuvants for use in the invention (N/A means, with respect tocharacterising data, that the data was not obtained) Com- ¹H-NMR data:pound (ppm/number of No. Structure Hs/multiplicity)  1

N/A  2

N/A  3

N/A  4

N/A  5

N/A  6

N/A  7

N/A  8

7.35-7.15 (4H, m); 5.70 (1H, br); 3.40 (2H, m); 2.45 (3H, s); 1.55 (1H,m); 1.40 (2H, m); 1.35-1.25 (6H, m); 1.00-0.90 (6H, m).  9

7.35-7.25 (2H, m); 7.20-7.15 (2H, m); 5.80 (1H, br); 3.40 (2H, m); 2.45(3H, s); 1.60 (2H, m); 1.35 (4H, m); 0.95 (3H, t). 10

(complex due to restricted rotation) 7.30-7.10 (4H, m); 5.05 & 3.75 (1H,2m); 3.00 & 2.65 (3H, 2 s); 2.30 (3H, 2s); 1.15 & 1.10 (6H, d and m). 11

7.30-7.15 (4H, m); 3.60-3.20 (2H, br); 3.10-2.85 (2H, br); 2.30 (3H, s);2.15 (1H, m); 1.85 (1H, m) 1.00 (6H, d); 0.75 (6H, d). 12

(complex due to restricted rotation) 7.30-7.10 (4H, m); 3.55 and 3.05(2H, br and t); 3.10 and 2.80 (3H, 2s); 2.30 (3H, 2s); 1.70 and 1.50(2H, 2m); 1.00 and 0.75 (3H, 2t). 13

7.25-7.10 (4H, m); 2.75 (3H, s); 2.30 (3H, s); 1.55 (9H, s). 14

(complex due to restricted rotation) 7.30-7.15 (4H, m); 3.80-3.20 (2H,br); 3.15 and 3.05 (2H, 2m); 2.30 (3H, 2s); 1.70, 1.45 and 1.10 (4H,3m); 1.25, 1.05, 1.00 and 0.75 (6H, 4t). 15

(complex due to restricted rotation) 7.30-7.10 (4H, m); 3.80-3.10 (2H,br); 3.05 (2H, m); 2.30 (3H, s); 1.70, 1.45 and 1.10 (6H, 3m); 1.00 (3H,m); 0.75 (3H, m). 16

(complex due to restricted rotation) 7.30-7.15 (4H, m); 3.55 and 3.10(2H, br and t); 3.10 and 2.80 (3H, 2s); 2.30 (3H, s); 1.70, 1.50,1.40-1.35, 1.20 and 1.10 (6H, 5m); 0.95 and 0.80 (3H, 2t). 17

7.30-7.15 (4H, m); 3.80-3.20 (2H, br); 3.00 (2H, br); 2.30 (3H, s); 1.70(2H, m); 1.50 (2H, m); 1.00 (3H, t); 0.75 (3H, t). 18

(complex due to restricted rotation) 7.30-7.10 (4H, m); 3.55 and 3.10(2H, br and t); 3.10 and 2.80 (3H, 2s); 2.30 (3H, s); 1.65, 1.50-1.40and 1.15 (4H, 3m); 1.00 and 0.80 (3H, 2t).

As stated above, certain compounds of formula (I) are novel. One groupof such novel compounds are those wherein the sum of m and n is three orgreater. Also novel are compounds of formula (I)

wherein m is an integer of 1, 2, or 3; n is an integer of 1, 2, or 3; R¹is C(O)NR³R⁴; each R² is independently C₁₋₁₅ alkyl, each R³ isindependently H, or C₁₋₆ alkyl, each R⁴ is independently C₁₋₈ alkyl, orthe group-[AO]_(x)—R⁵, wherein x is an integer of 0 to 12, each A isindependently C₁₋₄ alkyl, and each R⁵ is independently C₁₋₄ alkyl, orNH₂; provided that when m is 1 and n is 1: (i) when R² is methyl in themeta position then R³ is not ethyl when R⁴ is ethyl, and R³ is notmethyl when R⁴ is methyl; (ii) when R² is methyl in the ortho positionthen: R³ is not methyl when R⁴ is propyl or tert-butyl, R³ is notn-propyl when R⁴ is ethyl, n-propyl, or n-butyl, R³ is not n-butyl whenR⁴ is methyl, ethyl or n-butyl, R³ is not iso-butyl when R⁴ isiso-butyl, R⁴ is not methyl when R³ is H, propyl, tert-butyl, orn-pentyl, R⁴ is not n-propyl when R³ is ethyl, R⁴ is not n-butyl when R³is ethyl, R⁴ is not pentyl when R³ is H or methyl, R⁴ is not2-ethyl-hexyl when R³ is H or methyl; and (iii) when R² is methyl at thepara position or ethyl at the ortho position, R³ and R⁴ are not bothmethyl.

Also novel are compounds of formula (I)

wherein m is an integer of 1, 2, or 3; n is an integer of 0, 1, 2, or 3;R¹ is C(O)NR³R⁴; each R² is independently C₁₋₁₅ alkyl, each R³ isindependently H, or C₁₋₆ alkyl, each R⁴ is independently C₁₋₈ alkyl, orthe group-[AO]_(x)—R⁵, wherein x is an integer of 0 to 20, each A isindependently C₁₋₄ alkyl, and each R⁵ is independently H, C₁₋₄ alkyl, orNH₂ provided that at least one R⁴ is the group-[AO]_(x)—R⁵.

Also novel are compounds of formula (I)

wherein m is an integer of 1, 2, or 3; n is an integer of 0, 1, 2, or 3;R¹ is C(O)NR³R⁴; each R² is independently C₁₋₁₅ alkyl, each R³ isindependently H, or C₁₋₆ alkyl, each R⁴ is independently C₁₋₈ alkyl, orthe group-[AO]_(x)—R⁵, wherein x is an integer of 0 to 20, each A isindependently C₁₋₄ alkyl, and each R⁵ is independently H, C₁₋₄ alkyl, orNH₂ provided that at least one R² group is in the para-position.

For compounds of the invention, preferences for the integers m, n and x,as well as for the substituents R¹, R², R³, R⁴, R⁵ and A are asdescribed hereinbefore.

Compounds of formula (I) as defined hereinbefore may either be obtainedcommercially e.g. Compound 1 (N,N-diethyl-3-methylbenzamide orN,N-diethyl-m-toluamide may be obtained from Alfa Aesar US or CarboneScientific UK) or easily synthesised from readily available startingmaterial using routine techniques known in the art (with respect toCompound 1, see for example Wang, B. J-S., 1974 J. Chem. Ed. 51(10):631), or as described hereinafter and in the Examples.

In general compounds of formula (I) may be prepared according toreaction scheme 1 below:

Benzoic acid derivatives of formula (II) (wherein R² and n are asdefined herein) can be converted to acid chlorides of formula (III)using for example thionyl chloride. The acid chloride can be reactedwith a primary or secondary amine (wherein R³ and R⁴ are as definedherein) to form the aromatic amide of choice. The skilled man willappreciate that polyethylene, or other polyalkyl- or mixed polyalkyl-,mono- or di-amines can be used as the amine. Compounds of formula (II)and suitable amines are readily available or may be synthesised usingroutine techniques with which the skilled man is familiar.

As stated previously, the present invention is based on the unexpectedfinding that compounds of formula (I) are particularly good adjuvants,in particular in agrochemical formulations, and a particular feature ofthe adjuvancy exhibited by the compounds of formula (I) is their abilityto enhance bioefficacy. Accordingly, such adjuvants may be combined withan active ingredient, which is an agrochemical, in order to form anagrochemical composition. The present invention extends to suchagrochemical compositions as well as to a method of making such anagrochemical composition, wherein said method comprises combining acompound of formula (I) with an agrochemical. The noun “agrochemical” asused herein incorporates herbicides, insecticides, nematicides,molluscicides, funcgicides, plant growth regulators, and safeners. Asshown herein, compounds of formula (I) are particularly efficacious asadjuvants in herbicidal compositions.

The term adjuvant as used herein refers to a compound which is capableof enhancing the biological activity of an active ingredient (inparticular an agrochemical). Thus, the biological activity of acomposition comprising an adjuvant and an active ingredient will begreater than the biological activity of the active ingredient in theabsence of the adjuvant. This may be evidenced by directly comparing thebiological activity of a composition comprising an agrochemical andadjuvant according to the invention with the biological activity of theagrochemical in the absence of said adjuvant. Alternatively, it may alsobe evidenced by comparing the biological activity of a compositioncomprising an agrochemical and an adjuvant according to the inventionwith the biological activity of the agrochemical in combination with aknown adjuvant. In some cases, the observed efficacy of the combinationof ingredients according to the invention can sometimes be significantlyhigher than that which would be expected from the individual ingredientsused (i.e. synergism may be observed).

Suitable herbicides include bicyclopyrone, mesotrione, fomesafen,tralkoxydim, napropamide, amitraz, propanil, pyrimethanil, dicloran,tecnazene, toclofos methyl, flamprop M, 2,4-D, MCPA, mecoprop,clodinafop-propargyl, cyhalofop-butyl, diclofop methyl, haloxyfop,quizalofop-P, indol-3-ylacetic acid, 1-naphthylacetic acid, isoxaben,tebutam, chlorthal dimethyl, benomyl, benfuresate, dicamba, dichlobenil,benazolin, triazoxide, fluazuron, teflubenzuron, phenmedipham,acetochlor, alachlor, metolachlor, pretilachlor, thenylchlor, alloxydim,butroxydim, clethodim, cyclodim, sethoxydim, tepraloxydim,pendimethalin, dinoterb, bifenox, oxyfluorfen, acifluorfen,fluoroglycofen-ethyl, bromoxynil, ioxynil, imazamethabenz-methyl,imazapyr, imazaquin, imazethapyr, imazapic, imazamox, flumioxazin,flumiclorac-pentyl, picloram, amodosulfuron, chlorsulfuron,nicosulfuron, rimsulfuron, triasulfuron, triallate, pebulate,prosulfocarb, molinate, atrazine, simazine, cyanazine, ametryn,prometryn, terbuthylazine, terbutryn, sulcotrione, isoproturon, linuron,fenuron, chlorotoluron and metoxuron.

Suitable fungicides include isopyrazam, mandipropamid, azoxystrobin,trifloxystrobin, kresoxim methyl, famoxadone, metominostrobin andpicoxystrobin, cyprodanil, carbendazim, thiabendazole, dimethomorph,vinclozolin, iprodione, dithiocarbamate, imazalil, prochloraz,fluquinconazole, epoxiconazole, flutriafol, azaconazole, bitertanol,bromuconazole, cyproconazole, difenoconazole, hexaconazole,paclobutrazole, propiconazole, tebuconazole, triadimefon,trtiticonazole, fenpropimorph, tridemorph, fenpropidin, mancozeb,metiram, chlorothalonil, thiram, ziram, captafol, captan, folpet,fluazinam, flutolanil, carboxin, metalaxyl, bupirimate, ethirimol,dimoxystrobin, fluoxastrobin, orysastrobin, metominostrobin andprothioconazole.

Suitable insecticides include thiamethoxam, imidacloprid, acetamiprid,clothianidin, dinotefuran, nitenpyram, fipronil, abamectin, emamectin,bendiocarb, carbaryl, fenoxycarb, isoprocarb, pirimicarb, propoxur,xylylcarb, asulam, chlorpropham, endosulfan, heptachlor, tebufenozide,bensultap, diethofencarb, pirimiphos methyl, aldicarb, methomyl,cyprmethrin, bioallethrin, deltamethrin, lambda cyhalothrin,cyhalothrin, cyfluthrin, fenvalerate, imiprothrin, permethrin andhalfenprox.

Suitable plant growth regulators include paclobutrazole and1-methylcyclopropene.

Suitable safeners include benoxacor, cloquintocet-mexyl, cyometrinil,dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim,mefenpyr-diethyl, MG-191, naphthalic anhydride, and oxabetrinil.

Of course, the various editions of The Pesticide Manual [especially the14^(th) and 15^(th) editions] and the also disclose details ofagrochemicals, any one of which may suitably be used with the presentinvention.

The skilled man will appreciate that compositions of the invention maycomprise one or more of the agrochemicals as described above.

Compositions of the invention will typically comprise the agrochemicalin an amount that is recommended in the art. Typically a compound offormula (I) will comprise from about 0.0005% to about 90% v/v of thetotal composition.

The skilled man will appreciate that compositions of the invention maybe in the form of a ready-to-use formulation or in concentrate formsuitable for further dilution by the end user, and the concentration ofagrochemical and compound of formula (I) will be adjusted accordingly.In concentrated form, compositions of the invention typically compriseagrochemical at 5 to 75% v/v, more preferably 10 to 50% v/vagrochemical. Ready-to-use compositions of the invention will typicallycomprise from 0.0001% to 1% v/v, more preferably from 0.001% to 0.5%v/v, and more preferably still from 0.001% to 0.1% v/v agrochemical.

Typically a compound of formula (I) will comprise from about 0.0005% toabout 90% v/v of the total composition. Where the density of theadjuvant is approximately 1 the skilled man will appreciate measurementsof v/v approximate measurements of w/v and typically v/v is a moreappropriate measure where the compound of formula (I) is a liquid. Inconcentrated form, compositions of the invention typically comprise acompound of formula (I) from 1% to 80% (v/v or w/v) preferably from 5%to 60% (v/v or w/v) and more preferably from 10% (w/v or v/v) to 40%(w/v or v/v). Ready to use compositions of the invention typicallycomprise a compound of formula (I) from about 0.05% to about 1% w/v (orv/v) of the total composition, more preferably still from about 0.1% toabout 0.5% w/v (or v/v) of the total composition. In specificembodiments the aromatic ester will be included at concentrations of0.1%, 0.2%, 0.25%, 0.3%, 0.4% or 0.5% w/v (or v/v) of the totalcomposition.

Compounds of formula (I) may be manufactured and/or formulatedseparately, and in order to be used as an adjuvant these may be added toa separate agrochemical formulation at a subsequent stage, typicallyimmediately prior to use.

Compositions of the invention may be formulated in any suitable mannerknown to the man skilled in the art. As mentioned above, in one form acomposition of the invention is a formulation concentrate which may bediluted or dispersed (typically in water) by an end-user (typically afarmer) in a spray tank prior to application.

Additional formulation components may be incorporated alongsidecompounds of formula (I) or compositions of the invention in suchformulations. Such additional components include, for example,adjuvants, surfactants, emulsifiers, and solvents, and are well known tothe man skilled in the art: standard formulation publications disclosesuch formulation components suitable for use with the present invention(for example, Chemistry and Technology of Agrochemical Formulations, Ed.Alan Knowles, published by Kluwer Academic Publishers, The Netherlandsin 1998; and Adjuvants and Additives: 2006 Edition by Alan Knowles,Agrow Report DS256, published by Informa UK Ltd, December 2006). Furtherstandard formulation components suitable for use with the presentinvention are disclosed in WO2009/130281A1 (see from page 46, line 5 topage 51, line 40).

Thus, compositions of the present invention may also comprise one ormore surfactants or dispersing agents to assist the emulsification ofthe agrochemical on dispersion or dilution in an aqueous medium(dispersant system). The emulsification system is present primarily toassist in maintaining the emulsified agrochemical in water. Manyindividual emulsifiers, surfactants and mixtures thereof suitable forforming an emulsion system for an agrochemical are known to thoseskilled in the art and a very wide range of choices is available.Typical surfactants that may be used to form an emulsifier systeminclude those containing ethylene oxide, propylene oxide or ethyleneoxide and propylene oxide; aryl or alkylaryl sulphonates andcombinations of these with either ethylene oxide or propylene oxide orboth; carboxylates and combinations of these with either ethylene oxideor propylene oxide or both. Polymers and copolymers are also commonlyused.

Compositions of the present invention may also include solvents, whichmay have a range of water solubilitites. Oils with very low watersolubilities may be added to the solvent of the present invention forassorted reasons such as the provision of scent, safening, costreduction, improvement of the emulsification properties and alterationof the solubilising power. Solvents with higher water solubility mayalso be added for various reasons, for instance to alter the ease withwhich the formulation emulsifies in water, to improve the solubility ofthe pesticide or of the other optional additives in the formulation, tochange the viscosity of the formulation or to add a commercial benefit.

Other optional ingredients which may be added to the formulation includefor example, colourants, scents, and other materials which benefit atypical agrochemical formulation.

Compounds and/or compositions of the invention may formulated forexample, as emulsion or dispersion concentrates, emulsions in water oroil, as microencapsulated formulations, aerosol sprays or foggingformulations; and these may be further formulated into granularmaterials or powders, for example for dry application or aswater-dispersible formulations. Preferably compositions of the inventionwill be formulated as, or comprised by a microcapsule.

Compositions of the invention may be used to control pests. The term“pest” as used herein includes insects, fungi, molluscs, nematodes, andunwanted plants. Thus, in order to control a pest a composition of theinvention may be applied directly to the pest, or to the locus of apest.

Compositions of the invention also have utility in the seed treatmentarena, and thus may be applied as appropriate to seeds.

The skilled man will appreciate that the preferences described abovewith respect to various aspects and embodiments of the invention may becombined in whatever way is deemed appropriate.

Various aspects and embodiments of the present invention will now beillustrated in more detail by way of example. It will be appreciatedthat modification of detail may be made without departing from the scopeof the invention.

EXAMPLE 1 Synthesis of4-Dodecyl-N-[2-(2-{2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-benzamide(Compound No. 2)

4-Dodecyl-N-(2-{2-[2-(2-{2-[2-(2-ethoxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-benzamide(Compound 2 in Table 1 above) was synthesised by reactingpara-dodecylbenzoic acid with octaethylene oxide amine, usingN,N′-dicyclohexylcarbodiimide (DCC) as a coupling agent.

EXAMPLE 2 Use of4-Dodecyl-N-[2-(2-{2-[2-(2-{2-[2-(2-hydroxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethyl]-benzamide(Compound No. 2) as an Adjuvant in Nicosulfuron Formulations

Compound No. 2 (see Example 1 and Table 1 above) was tested in aglasshouse against four weed species in combination with the herbicidenicosulfuron. An agrochemical composition was prepared containing 0.2%v/v of the adjuvant in a track sprayer and was applied at a volume of200 litres per hectare. Nicosulfuron was applied at either 30 or 60grams of pesticide per hectare on weeds which had been grown to the 1.3or 1.4 leaf stage. The weed species were Chenopodium album (CHEAL),Abutilon theophrasti (ABUTH), Brassica perenni (BRAPP), and Digitariasanguinalis (DIGSA).

Each spray test was replicated three times. The efficacy of theherbicide was assessed visually and expressed as a percentage of theleaf area killed. Samples were assessed at time periods of 7, 14 and 21days following application. The results shown in Table 2 below are meanaverages over the two rates of nicosulfuron, three replicates and thethree assessment timings. The results are compared to those obtained fornicosulfuron in combination with the commercially available tank mixadjuvant Turbocharge® D (Syngenta Crop Protection Canada, Inc.), and itcan be seen in each case superior weed control is observed when Compound2 is included in the formulation as an adjuvant.

TABLE 2 Mean percentage kill results for nicosulfuron in the presence ofcompound no. 2 compared to nicolsulfuron in the presence ofTurbocharge ® D. Adjuvant CHEAL ABUTH BRAPP DIGSA Mean (g/ha) CompoundNo 2 80 47.1 86.4 83.1 73.9 Turbocharge 76.7 41.7 80.6 64.8 65.9

EXAMPLE 3 Use of Compound No. 2 as an Adjuvant for Fomesafen

Compound No. 2 was tested in a glasshouse against four weed species incombination with the herbicide fomesafen. An agrochemical compositionwas prepared containing 0.2% v/v of the adjuvant in a track sprayer andwas applied at a volume of 200 litres per hectare. Fomesafen was appliedat either 60 or 120 grams of pesticide per hectare on weeds which hadbeen grown to the 1.3 or 1.4 leaf stage. The weed species wereChenopodium album (CHEAL), Abutilon theophrasti (ABUTH), Setaria viridis(SETVI), and Xanthium strumarium (XANST).

Each spray test was replicated six times. The efficacy of the herbicidewas assessed visually and expressed as a percentage of the leaf areakilled. Samples were assessed at time periods of 7 and 14 days followingapplication. The results shown in Table 3 below are mean averages overthe two rates of fomesafen, six replicates and the two assessmenttimings, and are compared to the efficacy of fomesafen in the absence ofadjuvant.

TABLE 3 Mean percentage kill results for fomesafen in the presence andabsence of compound 2 Mean across Adjuvant ABUTH CHEAL SETVI XANSTspecies Compound 2 90 34.1 41.7 68.8 58.6 None 60.8 43.3 38.2 45.8 47.0

EXAMPLE 4 Use of Compound 2 as an Adjuvant for Mesotrione

Compound No. 2 was tested in a glasshouse against four weed species incombination with the herbicide mesotrione. An agrochemical compositionwas prepared containing 0.2% v/v of the adjuvant in a track sprayer andwas applied at a volume of 200 litres per hectare. Mesotrione wasapplied at either 60 or 120 grams of pesticide per hectare on weedswhich had been grown to the 1.3 or 1.4 leaf stage. The weed species wereAmaranthus retroflexus (AMARE), Abutilon theophrasti (ABUTH), Brachiariaplatyphylla (BRAPP), and Digitaria sanguinalis (DIGSA).

Each spray test was replicated six times. The efficacy of the herbicidewas assessed visually and expressed as a percentage of the leaf areakilled. Samples were assessed at time periods of 6, 14 and 21 daysfollowing application. The results shown in Table 4 below are meanaverages over the two rates of mesotrione, six replicates and the threeassessment timings. The results are compared to those obtained formesotrione in combination with the commercially available tank mixadjuvant Turbocharge® D (Syngenta Crop Protection Canada, Inc.).

TABLE 4 Mean percentage kill results for nicosulfuron in the presence ofcompound 2 compared to nicolsulfuron in the presence of Turbocharge ® D.Mean across Adjuvant AMARE ABUTH BRAPP DIGSA species Compound 2 63.573.3 68.2 83.4 72.1 Turbocharge 67.2 73.8 58.2 79.7 69.8

EXAMPLE 5 Use of Compound 1 (N,N-diethyl-3-methylbenzamide) as anAdjuvant for Fomesafen

Compound 1 (N,N-diethyl-3-methylbenzamide) was tested in a glasshouseagainst four weed species using the herbicide fomesafen. An agrochemicalcomposition was prepared containing 0.2% v/v of the adjuvant in a tracksprayer and was applied at a volume of 200 litres per hectare. Fomesafenwas applied at either 60 or 120 grams of pesticide per hectare on eachof the weed species. The weed species and their growth stage at sprayingwere Chenopodium album (CHEAL; growth stage 13/14), Abutilon theophrasti(ABUTH; growth stage 12), Setaria viridis (SETVI; growth stage 13), andXanthium strumarium (XANST; growth stage 12).

Each spray test was replicated three times. The efficacy of theherbicide was assessed visually and expressed as a percentage of theleaf area killed. Samples were assessed at time periods of 7, 14 and 21days following application. The results shown in Table 5 below are meanaverages over the two rates of fomesafen, three replicates and the threeassessment timings, and are compared to the efficacy of fomesafen in theabsence of adjuvant.

TABLE 5 Mean percentage kill results for fomesafen in the presence andabsence of compound 1. Mean across Adjuvant CHEAL ABUTH SETVI XANSTspecies Compound 1 80.3 38.9 15.8 35.6 42.6 None 77.5 20 10.6 42.8 37.7

EXAMPLE 6 Use of Compound 1 as an Adjuvant for Mesotrione

Compound 1 was tested in a glasshouse against four weed species usingthe herbicide mesotrione. A 20% w/w stock emulsion of compound 1 wasprepared additionally containing 2% w/w Gohsenol®GLO3 and 2% w/wPluronic®PE10500 as surfactants. Using this, an agrochemical compositionwas prepared containing 0.2% v/v of the adjuvant in a track sprayer andwas applied at a volume of 200 litres per hectare. Mesotrione wasapplied at either 45 or 90 grams of pesticide per hectare on each of theweed species. The weed species and their growth stage at spraying wereAmaranthus tuberculatus (AMATE; growth stage 13/14), Brachiariadecumbens (BRADE; growth stage 13/14), Digitaria sanguinalis (DIGSA;growth stage 14), and Polygonum convolvulus (POLCO; growth stage11/11.5).

Each test was replicated three times. The efficacy of the herbicide wasassessed visually and expressed as a percentage of the leaf area killed.Samples were assessed at time periods of 7, 14 and 21 days followingapplication. The results shown in Table 6 below are mean averages overthe two rates of mesotrione, three replicates and the three assessmenttimings, and are compared to the efficacy of mesotrione in absence ofadjuvant.

TABLE 6 Mean percentage kill results for mesotrione in the presence andabsence of compound 1. Mean across Adjuvant AMATE BRADE DIGSA POLCOspecies Compound 1 71.7 28.9 28.6 87.2 54.1 None 65.6 26.7 23 73.3 47.1

EXAMPLE 7 Use of Compound 1 as an Adjuvant for Nicosulfuron

Compound 1 was tested in a glasshouse against four weed species usingthe herbicide nicosulfuron. A 20% w/w stock emulsion of compound 1 wasprepared additionally containing 2% w/w Gohsenol®GLO3 and 2% w/wPluronic®PE10500 as surfactants. Using this, an agrochemical compositionwas prepared containing 0.2% v/v of the adjuvant in a track sprayer andwas applied at a volume of 200 litres per hectare. Nicosulfuron wasapplied at either 30 or 60 grams of pesticide per hectare on each of theweed species. The weed species and their growth stage at spraying wereAbutilon theophrasti (ABUTH; growth stage 13), Chenopodium album (CHEAL;growth stage 14), Digitaria sanguinalis (DIGSA; growth stage 13), andSetaria viridis (SETVI; growth stage 13).

Each spray test replicated three times. The efficacy of the herbicidewas assessed visually and expressed as a percentage of the leaf areakilled. Samples were assessed at time periods of 14 and 21 daysfollowing application. The results shown in Table 7 below are meanaverages over the two rates of nicosulfuron, three replicates and thetwo assessment timings, and are compared to the efficacy of nicosulfuronin the absence of an adjuvant.

TABLE 7 Mean percentage kill results for nicosulfuron in the presenceand absence of compound 1. Mean across Adjuvant ABUTH CHEAL DIGSA SETVIspecies Compound 1 72.9 63.8 89.4 93.4 81.3 None 69.2 50.8 87.9 92 75

EXAMPLE 8 Use of Compound 1 as an Adjuvant for Pinoxaden

The adjuvant shown in example 1 was tested in a glasshouse against fourweed species in combination with the herbicide pinoxaden. A 20% w/wstock emulsion of compound 1 was prepared additionally containing 2% w/wGohsenol®GLO3 and 2% w/w Pluronic®PE10500 as surfactants. Using this, anagrochemical composition was prepared containing 0.2% v/v of theadjuvant in a track sprayer and was applied at a volume of 200 litresper hectare. Pinoxaden was applied at either 7.5 or 15 grams ofpesticide per hectare on each of the weed species. The weed species andtheir growth stage at spraying were Alopecurus myosuroides (ALOMY;growth stage 13), Avena fatua (AVEFA; growth stage 12); Lolium perenne(LOLPE; growth stage 13), Setaria viridis (SETVI; growth stage 14).

Each spray test was replicated three times. The efficacy of theherbicide was assessed visually and expressed as a percentage of theleaf area killed. Samples were assessed at time periods of 14 and 21days following application. The results shown in Table 8 are meanaverages over the two rates of pinoxaden, three replicates and the twoassessment timings, and are compared to the efficacy of pinoxaden in theabsence of adjuvant.

TABLE 8 Mean percentage kill results for pinoxaden in the presence andabsence of compound 1. Mean across Adjuvant ALOMY AVEFA LOLPE SETVIspecies Novel adjuvant 1 22.5 29.2 20.8 15.8 22.1 Pinoxaden 21.2 20.812.5 15 17.4

EXAMPLE 9 Production of Ethoxylated Aromatic Amides (Compounds 3, 4, 5,and 6)

Compounds 3, 4, 5, and 6 from table 1 above were prepared in thefollowing manner. Four samples of monoamines of polyethylene glycol (A,B, C, & D) were purchased from St Andrews chemicals, St AndrewsUniversity, St Andrews, Scotland. These were stated as having, 5, 10,15, and 20 ethylene oxide moieties respectively, but following nmpspectroscopic analysis were found to have the average number of ethyleneoxide moieties as shown in Table 9.

TABLE 9 Degree of ethoxylation of polyethylene glycol monoamine samplesas assessed by nmp spectroscopy. Sample Average no of EO unitsdetermined A: Monoethanolamine 4 EO 5 B: Monoethanolamine 9 EO 10.2 C:Monoethanolamine 14 EO 14.5 D: Monoethanolamine 19 EO 19.2

Each of these amines (A, B, C, and D) was used to produce an aromaticamide using the general methodology described below.

Monoethanolamine polyethylene oxide was added to a reaction flask withbenzoyl chloride and the solvent tetrahydrofuran. The flask was sealedand placed in a microwave reactor. The sample was heated to 140° C. and7 bar pressure for five minutes. Table 10 summarises reactant quantitiesand product yield for the individual reactions.

TABLE 10 Amide product PEG Benzoyl (with reference monoethanolaminechloride to Table 1 Amide sample (g) (g) THF (ml) above) yield % A(1.01) 0.687 5 Compound 3 85 B (1) 0.424 5 Compound 4 78 C (1) 0.239 5Compound 5 93 D (0.96) 0.216 5 Compound 6 76

The resulting amide products were purified by dissolution in acetonefollowed by precipitation with hexane. Product structures were checkedwith nmr spectroscopy and confirmed as those given in Table 1 above.

EXAMPLE 10 Production of an Ethoxylated Aromatic Amide

Benzoyl chloride was reacted with the diamine of polyethylene oxide withan average of 8 EO using the methodology described in Example 8 above.This formed an aromatic amide with the structure of Compound 7 as shownin Table 1 above.

EXAMPLE 11 Production of Ethoxy/Propoxylated Aromatic Amide

Benzoyl chloride was reacted with Jeffamine® ED600 (Huntsman PerformanceProducts, Texas, USA)

The Jeffamine® ED series of polyether amines are polyether diaminesbased on a predominantly PEG backbone. They have the followingrepresentative structure:

For Jeffamine® ED600 the characteristics are as follows: y ˜9.0, (x+z)˜3.6, molecular weight ˜600.

The reaction formed a mixed benzoate amide ester of thepolyethylene/polypropylene copolymer carrying a terminal amino group.The degree of ethoxylation and propoxylation is mixed, with the esterhaving on average 9EO moieties and on average 3.6 PO moieties.

1-17. (canceled)
 18. A compound of formula (I) for use as an adjuvant inan agrochemical composition comprising an agrochemical active ingredient

wherein m is 1; n is an integer of 0, 1, 2, or 3; R¹ is C(O)NR³R⁴; eachR² is independently C₁₋₁₅ alkyl, each R³ is independently H, or C₁₋₆alkyl, each R⁴ is independently C₁₋₈ alkyl, or the group-[AO]_(x)—R⁵wherein x is an integer of 0 to 20, each A is independently C₁₋₄ alkyl,and each R⁵ is independently H, C₁₋₄ alkyl, or NH₂.
 19. A compound offormula (I) as defined in claim 1 wherein R⁴ is the group-[AO]x-R⁵wherein A and R⁵ are as defined in claim 1 and x is an integer of 1 to19.
 20. A compound according to claim 19, wherein at least one R² is atthe para position.
 21. A compound according to claim 19, wherein: eachR² is independently methyl or C₆₋₁₂ alkyl; and wherein in at least oneR¹ and R³ is selected from the group consisting of H, methyl, ethyl,propyl or butyl; and R⁴ is the group-[AO]_(x)R⁵ wherein A is ethyl orpropyl and x is an integer of 7-18.
 22. An compound according to claim19, wherein in at least one R¹, R³ is H and R⁴ is the group

wherein ‘b’ has the value of 9 and the sum of ‘a’ and ‘c’ is 3 or
 4. 23.A compound according to claim 19, wherein n is
 1. 24. A compoundaccording to claim 19, wherein n is
 0. 25. An agrochemical compositioncomprising a compound as defined in claim 19, and an agrochemical activeingredient.
 26. An agrochemical composition according to claim 25,wherein the compound of formula (I) comprises from about 0.0005% toabout 90% w/v of the total composition.
 27. An agrochemical compositionaccording to claim 25, wherein the agrochemical is selected from thegroup consisting of: bicyclopyrone, mesotrione, fomesafen, tralkoxydim,napropamide, amitraz, propanil, pyrimethanil, dicloran, tecnazene,toclofos methyl, flamprop M, 2,4-D, MCPA, mecoprop,clodinafop-propargyl, cyhalofop-butyl, diclofop methyl, haloxyfop,quizalofop-P, indol-3-ylacetic acid, 1-naphthylacetic acid, isoxaben,tebutam, chlorthal dimethyl, benomyl, benfuresate, dicamba, dichlobenil,benazolin, triazoxide, fluazuron, teflubenzuron, phenmedipham,acetochlor, alachlor, metolachlor, pretilachlor, thenylchlor, alloxydim,butroxydim, clethodim, cyclodim, sethoxydim, tepraloxydim,pendimethalin, dinoterb, bifenox, oxyfluorfen, acifluorfen,fluoroglycofen-ethyl, bromoxynil, ioxynil, imazamethabenz-methyl,imazapyr, imazaquin, imazethapyr, imazapic, imazamox, flumioxazin,flumiclorac-pentyl, picloram, amodosulfuron, chlorsulfuron,nicosulfuron, rimsulfuron, triasulfuron, triallate, pebulate,prosulfocarb, molinate, atrazine, simazine, cyanazine, ametryn,prometryn, terbuthylazine, terbutryn, sulcotrione, isoproturon, linuron,fenuron, chlorotoluron, metoxuron, isopyrazam, mandipropamid,azoxystrobin, trifloxystrobin, kresoxim methyl, famoxadone,metominostrobin and picoxystrobin, cyprodanil, carbendazim,thiabendazole, dimethomorph, vinclozolin, iprodione, dithiocarbamate,imazalil, prochloraz, fluquinconazole, epoxiconazole, flutriafol,azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole,hexaconazole, paclobutrazole, propiconazole, tebuconazole, triadimefon,trtiticonazole, fenpropimorph, tridemorph, fenpropidin, mancozeb,metiram, chlorothalonil, thiram, ziram, captafol, captan, folpet,fluazinam, flutolanil, carboxin, metalaxyl, bupirimate, ethirimol,dimoxystrobin, fluoxastrobin, orysastrobin, metominostrobin,prothioconazole, thiamethoxam, imidacloprid, acetamiprid, clothianidin,dinotefuran, nitenpyram, fipronil, abamectin, emamectin, bendiocarb,carbaryl, fenoxycarb, isoprocarb, pirimicarb, propoxur, xylylcarb,asulam, chlorpropham, endosulfan, heptachlor, tebufenozide, bensultap,diethofencarb, pirimiphos methyl, aldicarb, methomyl, cyprmethrin,bioallethrin, deltamethrin, lambda cyhalothrin, cyhalothrin, cyfluthrin,fenvalerate, imiprothrin, permethrin, halfenprox, paclobutrazole,1-methylcyclopropene, benoxacor, cloquintocet-mexyl, cyometrinil,dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim,mefenpyr-diethyl, MG-191, naphthalic anhydride, and oxabetrinil.
 28. Anagrochemical composition according to claim 25, wherein the compositionis formulated as, or comprised by a microcapsule.
 29. An agrochemicalcomposition according to claim 25, wherein the composition is anemulsion concentrate (EC) or dispersion concentrate (DC).
 30. Anagrochemical composition according to claim 25, comprising at least oneadditional component selected from the group consisting of anagrochemical, an adjuvant, a surfactant, an emulsifier, and a solvent.31. A method of controlling a pest, comprising applying a composition asdefined in claim 25 to said pest or the locus of said pest.
 32. A methodof making an agrochemical composition comprising providing: i. anagrochemical ii. and a compound of formula (I) as defined in claim 19;and combining the agrochemical, and compound of formula (I).
 33. Amethod according to claim 32, wherein the agrochemical is as defined inclaim
 27. 34. A method of increasing the efficacy of an agrochemicalcomprising combining a compound of formula (I) as defined in claim 18with said agrochemical.